Water-repellent fabrics

ABSTRACT

The present disclosure describes a method of manufacturing a natural textile with water repellent properties. Treatment of a natural textile with a composition of the invention provides water repellency to the treated textile.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority of U.S. Provisional Patent Application No. 62/065,505, filed on Oct. 17, 2014, and U.S. Provisional Patent Application No. 62/188,112, filed on Jul. 2, 2015, which are both hereby incorporated by reference herein in their entireties.

FIELD OF THE INVENTION

Embodiments of the present invention relate generally to the field of textiles, and, more specifically, to water-repellent fabrics.

BACKGROUND

Compositions that provide water repellency would help to maintain the durability, operability, and comfort of textiles. However, current compositions face challenges in maintaining water repellency for natural textiles.

BRIEF DESCRIPTION OF THE FIGURES

The present disclosure is illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings, in which:

FIG. 1 is a flow diagram illustrating a method of treating a textile with a composition in accordance with an embodiment of the present disclosure;

FIG. 2 is a flow diagram illustrating another method of treating a textile with a composition in accordance with an embodiment of the present disclosure;

FIG. 3 is a flow diagram illustrating another method of treating a textile with a composition in accordance with an embodiment of the present disclosure; and

FIG. 4 is a flow diagram illustrating another method of treating a textile with a composition in accordance with an embodiment of the present disclosure.

DETAILED DESCRIPTION

The embodiments of the present disclosure relate to compositions that impart desirable properties to textiles. The embodiments also provide a textile that is treated with such a composition, a method for making such composition, and a method of treating a textile with such a composition.

A textile can be treated with an additive that provides a property to the material or increases or improves a property of the textile relative to an analogous textile that has not been treated with a composition described herein. Non-limiting examples of properties provided or increased by the present embodiments include: water resistance; water repellence; hydrophobicity; softness; glide; soil-resistance; resistance to wear during washing/drying; abrasion resistance; and lower curing temperatures.

Textiles can be natural, synthetic, or semi-synthetic. The textiles can be of animal or plant origin, or can be purely synthetic. Non-limiting examples of textiles include fabrics, yarns, knits, fibers, clothing, garments, bedding, domestic linen, and upholstery. A textile can be treated prior with a coloring agent such as a dye or a pigment. Non-limiting examples of natural textiles include: burlap; calico; camel hair; canvas; cashmere; cheesecloth; chiffon; corduroy; cotton; denim; doeskin; double gauze; dowlas; drill; dugget; duck cloth; felt; fishnet; flannel; fleece; foulard; fur; fustian; gabardine; gauze; ghalamkar; haircloth; hemp; herringbone; himroo; hodden; jute; kemp; lace; lawn cloth; leather; textile linen; lensey-woolsey; longcloth; Mackinaw cloth; madapolam; madras; milliskin; mockado; mohair; moire; moleskin; monk's cloth; moquette; mouflon; muslin; natural grosgrain; natural melton; natural mesh; oilskin; organdy; organza; osnaburg; Ottoman; Oxford; paduasoy; polyester; pongee; poplin; quilting; Russel cord; satin; seersucker; sharkskin; silk; single gauze; spandex; suede; terrycloth; triple gauze; tweed; twill; velour; velvet; and wool. In certain embodiments, the textile is chosen from cotton and wool. Non-limiting examples of synthetic textiles include: Dyneema®; Gannex; Gore-Tex™; grosgrain; Kevlar™; synthetic melton; synthetic mesh; microfiber; milliskin; moire; Nomex™; nylon; rayon; silnylon; synthetic grosgrain; synthetic melton; synthetic mesh; and synthetic plush. Non-limiting examples of semi-synthetic textiles include: semi-synthetic grosgrain; semi-synthetic melton; semi-synthetic mesh; and semi-synthetic plush.

A textile could be a blend of natural, synthetic, or semi-synthetic textiles. The following non-limiting examples alternatively describe the ratio of a first textile and a second textile in the blend. The ratio can be: about 20 to about 1; about 19.9 to about 1; about 19.8 to about 1; about 19.7 to about 1; about 19.6 to about 1; about 19.5 to about 1; about 19.4 to about 1; about 19.3 to about 1; about 19.2 to about 1; about 19.1 to about 1; about 19 to about 1; about 18.9 to about 1; about 18.8 to about 1; about 18.7 to about 1; about 18.6 to about 1; about 18.5 to about 1; about 18.4 to about 1; about 18.3 to about 1; about 18.2 to about 1; about 18.1 to about 1; about 18 to about 1; about 17.9 to about 1; about 17.8 to about 1; about 17.7 to about 1; about 17.6 to about 1; about 17.5 to about 1; about 17.4 to about 1; about 17.3 to about 1; about 17.2 to about 1; about 17.1 to about 1; about 17 to about 1; about 16.9 to about 1; about 16.8 to about 1; about 16.7 to about 1; about 16.6 to about 1; about 16.5 to about 1; about 16.4 to about 1; about 16.3 to about 1; about 16.2 to about 1; about 16.1 to about 1; about 16 to about 1; about 15.9 to about 1; about 15.8 to about 1; about 15.7 to about 1; about 15.6 to about 1; about 15.5 to about 1; about 15.4 to about 1; about 15.3 to about 1; about 15.2 to about 1; about 15.1 to about 1; about 15 to about 1; about 14.9 to about 1; about 14.8 to about 1; about 14.7 to about 1; about 14.6 to about 1; about 14.5 to about 1; about 14.4 to about 1; about 14.3 to about 1; about 14.2 to about 1; about 14.1 to about 1; about 14 to about 1; about 13.9 to about 1; about 13.8 to about 1; about 13.7 to about 1; about 13.6 to about 1; about 13.5 to about 1; about 13.4 to about 1; about 13.3 to about 1; about 13.2 to about 1; about 13.1 to about 1; about 13 to about 1; about 12.9 to about 1; about 12.8 to about 1; about 12.7 to about 1; about 12.6 to about 1; about 12.5 to about 1; about 12.4 to about 1; about 12.3 to about 1; about 12.2 to about 1; about 12.1 to about 1; about 12 to about 1; about 11.9 to about 1; about 11.8 to about 1; about 11.7 to about 1; about 11.6 to about 1; about 11.5 to about 1; about 11.4 to about 1; about 11.3 to about 1; about 11.2 to about 1; about 11.1 to about 1; about 11 to about 1; about 10.9 to about 1; about 10.8 to about 1; about 10.7 to about 1; about 10.6 to about 1; about 10.5 to about 1; about 10.4 to about 1; about 10.3 to about 1; about 10.2 to about 1; about 10.1 to about 1; about 10 to about 1; about 9.9 to about 1; about 9.8 to about 1; about 9.7 to about 1; about 9.6 to about 1; about 9.5 to about 1; about 9.4 to about 1; about 9.3 to about 1; about 9.2 to about 1; about 9.1 to about 1; about 9 to about 1; about 8.9 to about 1; about 8.8 to about 1; about 8.7 to about 1; about 8.6 to about 1; about 8.5 to about 1; about 8.4 to about 1; about 8.3 to about 1; about 8.2 to about 1; about 8.1 to about 1; about 8 to about 1; about 7.9 to about 1; about 7.8 to about 1; about 7.7 to about 1; about 7.6 to about 1; about 7.5 to about 1; about 7.4 to about 1; about 7.3 to about 1; about 7.2 to about 1; about 7.1 to about 1; about 7 to about 1; about 6.9 to about 1; about 6.8 to about 1; about 6.7 to about 1; about 6.6 to about 1; about 6.5 to about 1; about 6.4 to about 1; about 6.3 to about 1; about 6.2 to about 1; about 6.1 to about 1; about 6 to about 1; about 5.9 to about 1; about 5.8 to about 1; about 5.7 to about 1; about 5.6 to about 1; about 5.5 to about 1; about 5.4 to about 1; about 5.3 to about 1; about 5.2 to about 1; about 5.1 to about 1; about 5 to about 1; about 4.9 to about 1; about 4.8 to about 1; about 4.7 to about 1; about 4.6 to about 1; about 4.5 to about 1; about 4.4 to about 1; about 4.3 to about 1; about 4.2 to about 1; about 4.1 to about 1; about 4 to about 1; about 3.9 to about 1; about 3.8 to about 1; about 3.7 to about 1; about 3.6 to about 1; about 3.5 to about 1; about 3.4 to about 1; about 3.3 to about 1; about 3.2 to about 1; about 3.1 to about 1; about 3 to about 1; about 2.9 to about 1; about 2.8 to about 1; about 2.7 to about 1; about 2.6 to about 1; about 2.5 to about 1; about 2.4 to about 1; about 2.3 to about 1; about 2.2 to about 1; about 2.1 to about 1; about 2 to about 1; about 1.9 to about 1; about 1.8 to about 1; about 1.7 to about 1; about 1.6 to about 1; about 1.5 to about 1; about 1.4 to about 1; about 1.3 to about 1; about 1.2 to about 1; about 1.1 to about 1; or about 1 to about 1.

In certain embodiments, a textile can have a threadcount of about 100, about 150, about 200, about 250, about 300, about 350, about 400, about 450, about 500, about 550, about 600, about 650, about 700, about 750, about 800, about 850, about 900, about 950, about 1000, about 1100, about 1200, about 1300, about 1400, about 1500, about 1600, about 1700, about 1800, about 1900, or about 2000.

In certain embodiments, a textile can have a threadcount from about 100 to about 150, from about 150 to about 200, from about 200 to about 250, from about 250 to about 300, 300 to about 350, from about 350 to about 400, from about 400 to about 450, from about 450 to about 500, 500 to about 550, from about 550 to about 600, from about 600 to about 650, from about 650 to about 700, 700 to about 750, from about 750 to about 800, from about 800 to about 850, from about 850 to about 900, 900 to about 950, from about 950 to about 1000, from about 1000 to about 1100, from about 1100 to about 1200, from about 1200 to about 1300, from about 1300 to about 1400, from about 1400 to about 1500, from about 1500 to about 1600, from about 1600 to about 1700, from about 1700 to about 1800, from about 1800 to about 1900, or from about 1900 to about 2000.

Treatment of a textile with a composition of the present embodiments can be performed manually or with a machine. Non-limiting examples of manual treatment include soaking, dripping, drenching, sponging, spraying, and brushing. Non-limiting examples of machines suitable for treatment include a dyeing machine, a washing machine, a spraying machine, and a cleaning drum of a dry cleaning machine. In certain embodiments, the dyeing machine is a rolling drum dyeing machine. In certain embodiments, the treatment comprises a dyeing process. Non-limiting examples of a dyeing process include solution dyeing, dope dyeing, spun dyeing, fiber dyeing, yarn dyeing, fabric dyeing, union dyeing, cross dyeing, product dyeing, and garment dyeing.

After treatment of a textile with a composition of the present embodiments, the textile can be dried. Non-limiting examples of drying include heating, hanging, or tumbling at about room temperature for at least about an hour, at about 150° C. for about 2 minutes, at about 160° C. for about 1 minute, and at about 170° C. for about 30 seconds. In certain embodiments, drying comprises use of a hydro extractor.

Textiles can be treated with additional rounds of, for example, from about 0.1 percent to about 5 percent by weight or from about 0.1 percent to about 3 percent by weight of solids of the composition of the present embodiments based on the weight of the textile to be treated. An aqueous liquor can be forcedly applied by padding in the desired concentration at wet pick-ups of, for example, from about 40 percent to about 100 percent by weight, subsequent pre-drying at, for example, from about 80° C. to about 110° C., and following hot treatment at, for example, from about 130° C. to about 170° C. for from about 1 minute to about 5 minutes. An exhaust process can also be used. Application can further be carried out by spray application, brush application, sponge application, drenching, or dripping.

A further aspect of the present disclosure is the use of the compositions, prepared according to certain embodiments, herein as a finish on flat textiles from organic solvents by drenching or dipping.

Revitalizing treatment of textiles cleaned in organic solvents can take place in a cleaning drum of a dry cleaning machine by pouring or spraying a liquor of the compositions, prepared according to certain embodiments, onto the solvent wet cleaned articles and subsequent removal of the solvents in a tumble dryer at elevated temperatures.

In embodiments of the present disclosure, a textile can be treated with composition comprising the following components: (1) polytetrafluoroethylene; (2) a hyperbranched dendrimer; and (3) a comb polymer.

Polytetrafluoroethylene (PTFE) is a high-molecular weight synthetic thermoplastic fluoropolymer of tetrafluoroethylene. PTFE is hydrophobic, and has fluorocarbon groups that exhibit reduced van der Waals forces. As PTFE is poorly soluble in many solvents, polymerization is conducted as an emulsion in water or using a surfactant such as perfluorooctanesulfonic (PFOS) acid. Properties of PTFE are shown in TABLE 1.

TABLE 1 TABLE 1: Physiochemical properties of PTFE Property Value Density 2200 kg/m³ Melting point 600 K Thermal expansion 112-125 × 10⁻⁶ K⁻¹ Thermal diffusivity 0.124 mm²/s Young's modulus 0.5 GPa Yield strength 23 MPa Bulk resistivity 1016 Ω · m Coefficient of friction 0.05-0.10 Dielectric constant ε = 2.1; tan(δ) < 5 × 10⁻⁴ Dielectric constant (60 Hz) ε = 2.1; tan(δ) < 2 × 10⁻⁴ Dielectric strength (1 MHz) 60 MV/m

Dendrimers are repetitively branched molecules. Dendrimers are monodisperse and can have a symmetric core with a core functional group with an outward three-dimensional spherical morphology. Non-limiting examples of dendrimers include low-molecular weight dendrimers, high-molecular weight dendrimers, hyperbranched dendrimers, and polymer brushes.

Dendrimer activity can be determined by the functional groups on the dendrimer surface, or through functional groups of the primary core. Dendrimers can be classified by generation, which is the number of repeated branching cycles performed during dendrimer synthesis. Higher generation dendrimers also have more exposed functional groups on the surface, which can later be used to customize the dendrimer for a given application. In certain embodiments, dendrimers can have average generation numbers of about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, about 18, about 19, about 20, about 21, about 22, about 23, about 24, or about 25. A composition of the present disclosure can comprise dendrimers with average generation numbers from about 1 to about 2, from about 2 to about 3, from about 3 to about 4, from about 4 to about 5, from about 5 to about 6, from about 6 to about 7, from about 7 to about 8, from about 8 to about 9, from about 9 to about 10, from about 10 to about 11, from about 11 to about 12, from about 12 to about 13, from about 13 to about 14, from about 14 to about 15, from about 15 to about 16, from about 16 to about 17, from about 17 to about 18, from about 18 to about 19, from about 19 to about 20, from about 20 to about 21, from about 21 to about 22, from about 22 to about 23, from about 23 to about 24, or from about 24 to about 25.

In certain embodiments, a dendrimer comprises a subunit of a partially-blocked or non-blocked di-, tri- or polyisocyanate with a compound having Formula (I) or Formula (II):

wherein R¹ is a hydrophobic residue having a form of —X—Y—Z or —Z, wherein X is —(CH₂)_(n)″—,

-   wherein Y is:

wherein Z is —(CH₂)_(m′)—CH₃,

-   wherein R² is a residue of the composition:

wherein R³ is a hydrophobic residue having a form of —X—Y—Z, —Z or —Y—Z, with the proviso that in the case of the —Y—Z meaning n″ replaces n in the R²residue,

-   wherein R⁴ is a residue having a form of —X—Y—Z or —(CH₂)_(n′)H, -   wherein B¹ is a hydrophobic residue having a form of —V—W—Z or —Z—,     wherein V is:

wherein W is selected from:

wherein B² is

wherein B³ is a hydrophobic residue, —V—W—Z, —Z, or

Each n is independently an integer 0, 1, or 2. Each n′ is independently an integer 0, 1, 2, 3, or 4. Each n″ is independently an integer 1, 2, 3, or 4. Each m is independently an integer 3, 4, 5, 6, 7, 8, 9, 10, or 11. Each m′ is independently an integer 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, or 26. In certain embodiments, the fraction of free isocyanate groups in the subunit is from about 1.8 per mole to about 10 per mole and the ratio of free isocyanate groups to reactive groups in the compounds of the formulae (I) or (II) is from about 1 to about 1 (˜1:-1) to about 1 to about 1.3 (˜1:˜1.3).

In certain embodiments, a textile can be treated with a composition comprising water and/or organic solvents and the following components: (1) about 10 to about 90 percent by weight of a fluorine containing oil- and water-repellent agent; (2) about 10 to about 80 percent by weight of a hydrophobic reaction product (S) obtainable by a reaction of Formula (I) or Formula (II); (3) 0-45 percent by weight of a blocked or non-blocked di-, tri- or polyisocyanate; and (4) optionally, an emulsifier.

Illustrative ranges are 20-80 percent by weight and or 25-65 percent by weight for component (1) and 20-80 percent by weight or 30-70 percent by weight for component (2). When component (3) is added, its concentration can be in the range of 1-35 percent by weight or in the range of 5-35 percent by weight. Emulsifiers can be between 4 and 25 percent by weight or between 5 and 15 percent by weight, based on the total of the active contents of the components (1), (2) and (3) used.

Component (1) of the composition uses a fluorine containing oil- and water-repellent composition. Compositions of component (1) use emulsions of a linear polymer having perfluorinated alkyl side residues and can be prepared from perfluoroalkylresidues-bearing monomers having copolymerization-capable fluorine-free monomers of different types.

Suitable polymers having perfluorinated alkyl side residues (e.g., component (1)) are obtained for example by emulsion copolymerization of monomers bearing perfluorinated alkyl residues, such as perfluoro-acrylate and/or -methacrylate, with fluorine-free monomers, for example butyl acrylate, stearyl acrylate, stearyl methacrylate, acrylonitrile, 2-hydroxyethyl acrylate, N-methylolacrylamide, N-methylolmethacrylamide or vinylidene chloride.

The addition of component (3) can be optional. The polyfunctionality of the polyisocyanate brings about a cross-linkage with the —OH, —COOH or —NH₂ groups present in most substrates and with unconverted functions of component (2), and this linkage can improve a garment's durability to washing operations and enhances resistance to abrasion.

Component (3) can be used in non-blocked form as well as in blocked form. The non-blocked forms of component (3) can be employed in applications from aprotic media, since doing so avoids any unwanted, premature reaction of the free NCO groups.

Non-limiting examples of non-blocked di-, tri- or polyisocyanates suitable for preparing component (3) and also the cyclized oligo- and polyisocyanates include those described above in relation to the composition of reaction product (S) in component (2).

When component (3) is to be applied to textiles from protic media, protection the reactive NCO groups by blocking them with suitable blocking agents can be performed. In these cases, component (3) is prepared by processes wherein the complete blocking of the free NCO groups of di-, tri- or polyisocyanates is carried out with a blocking agent and in the presence or absence of an organic solvent. Employment of a small stoichometric excess of blocking agent can facilitate complete blocking. When products for aqueous applications are to be prepared, the blocked di-, tri- or polyisocyanates, which can be dissolved in an organic solvent, can be converted into emulsion form through use of suitable emulsifiers.

Component (3) can be added in cases where the treated flat materials have to meet particularly high wash-stability requirements. 5-35% of this compound can be employed, and can be used, for example, directly and without formulation auxiliaries when application is to take place from waterless solvent-borne media. For application from an aqueous medium, emulsions of component (3) can be used, which have a solids content of, for example, 15-35 percent by weight, and which are prepared by using emulsifiers based on ethoxylated fatty amines, optionally in quaternary form, and optionally other emulsifying auxiliaries, for example, solubilizers based on ethylene glycol, 1,2-propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, mono- or diethylene glycol monobutyl ether, or N-methylpyrrolidone. Emulsification can be effected by high pressure homogenizing machines.

Comb polymers are polymers in which the main chain has at least one branch chain per repeat unit. In certain embodiments, the comb polymer comprises a main chain with at least two three-way chains comprising branch chains or linear chains. In certain embodiments, the comb polymer is a regular comb polymer if the branch chains and linear chains are identical in each repeating unit. In certain embodiments, the comb polymer chains are hydrocarbon chains. In certain embodiments, the hydrocarbon chains are alkylene, alkenylene, or alkynylene chains. In certain embodiments, the hydrocarbon chains comprise a functional group selected from: ether, ester, amide, amine, carbonyl, ketone, acetic anhydride, carbamate, thioether, carbonate, sulfone, cycloalkyl, cycloalkenyl, cycloalkynyl, cycloheteroalkyl, cycloheteroalkenyl, cycloheteroalkynyl, aryl, and heteroaryl, any of which is substituted or unsubstituted.

In certain embodiments, the hydrocarbon chains each have independently 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms, 12 carbon atoms, 13 carbon atoms, 14 carbon atoms, 15 carbon atoms, 16 carbon atoms, 17 carbon atoms, 18 carbon atoms, 19 carbon atoms, 20 carbon atoms, 21 carbon atoms, 22 carbon atoms, 23 carbon atoms, 24 carbon atoms, 25 carbon atoms, 26 carbon atoms, 27 carbon atoms, 28 carbon atoms, 29 carbon atoms, or 30 carbon atoms.

In certain embodiments, an average number of carbon atoms for hydrocarbon chains may range from about 6 carbon atoms to about 7 carbon atoms, from about 7 carbon atoms to about 8 carbon atoms, from about 8 carbon atoms to about 9 carbon atoms, from about 9 carbon atoms to about 10 carbon atoms, from about 10 carbon atoms to about 11 carbon atoms, from about 11 carbon atoms to about 12 carbon atoms, from about 12 carbon atoms to about 13 carbon atoms, from about 13 carbon atoms to about 14 carbon atoms, from about 15 carbon atoms to about 16 carbon atoms, from about 16 carbon atoms to about 17 carbon atoms, from about 17 carbon atoms to about 18 carbon atoms, from about 18 carbon atoms to about 19 carbon atoms, from about 19 carbon atoms to about 20 carbon atoms, from about 20 carbon atoms to about 21 carbon atoms, from about 21 carbon atoms to about 22 carbon atoms, from about 22 carbon atoms to about 23 carbon atoms, from about 23 carbon atoms to about 24 carbon atoms, from about 24 carbon atoms to about 25 carbon atoms, from about 25 carbon atoms to about 26 carbon atoms, from about 26 carbon atoms to about 27 carbon atoms, from about 27 carbon atoms to about 28 carbon atoms, from about 28 carbon atoms to about 29 carbon atoms, or from about 29 carbon atoms to about 30 carbon atoms.

In certain embodiments, the comb polymer is modified with a wax. Non-limiting examples of waxes include wax esters, paraffin waxes, hydrocarbon waxes, alkane waxes, alkene waxes, esterified waxes, saponified waxes, amide waxes, α-olefin waxes, polyolefin waxes, and polyethylene waxes.

Non-limiting examples of formulations of the hyperbranched dendrimer and comb polymer of a composition of the present disclosure include: RUCO-GUARD®; RUCO DRY ECO®; RUCO DRY DFY®; RUCO DRY DFE®; RUCO DRY DHY®; RUCO PHOB PZN CONC®; RUCO LINK ROM; BIONIC-FINISH®; BIONIC-FINISH C6®; and BIONIC-FINISH ECO®.

RUCO DRY ECO® is a cationic hyperbranched dendrimer formulation. The hyperbranched dendrimer is a hydrophobically-modified hyperbranched polyurethane dendrimer with wax-modified comb polymers, having a dendrimer surface with externally-oriented methyl groups. RUCO DRY ECO® can be provided as a white emulsion with a specific gravity of 1 g/mL at 20° C. The emulsion can have a pH value from about 3.5 to about 5.5. RUCO DRY ECO® can be formulated in water at various temperatures and concentrations.

RUCO DRY ECO® exhibits limited toxicity in an aqueous solution. The effective lethal concentration 50% (EC₅₀) in bacteria is greater than about 100 milligrams per liter (mg/L). The lethal concentration 50% (LC50) in fish is greater than about 100 mg/L. The oral lethal dose 50% (LD₅₀) in rats is greater than about 5000 milligrams per kilogram (mg/kg).

In certain embodiments, the composition is free of waxes and wax mixtures.

In certain embodiments, the composition is free of halogenated organic compounds, free of alkylphenol ethoxylates, free of organic solvent, and non-flammable.

In the case of use as a finish on fabrics, garments, or textiles, the composition can endow the textiles treated with durable oil- and water-repellent properties and also softness.

Further compositions useful for the PTFE component include emulsions comprising polyurethanes with laterally arranged PTFE chains. These compositions can be produced, for example, by reacting diisocyanates with PTFE-group-containing dialcohols in the presence of a catalyst system based on organic tin compounds and amines, for example a combination of dibutyltin dioctoate and trimethylamine. To improve overall properties, comonomers, for example N-methyldiethanolamine, can be incorporated in the polyurethane polymer chain in order, for example, that a cationic charge is generated for the polymer structure.

PTFE can be prepared using solubilizers, for example ethylene glycol, 1,2-propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, mono- or diethylene glycol monobutyl ether. In such cases, these solubilizers can also be present in the composition of the present invention even when based on water.

In certain embodiments, the dendrimer subunit comprises a compound and a di-, tri- or polyisocyanate. The compounds having Formula (I) which are used in the hyperbranched dendrimer can be reaction products of polyhydroxy alcohols (al) with carboxylic acids (bl) or with alkyl isocyanates (b2). Non-limiting examples of polyhydroxy alcohols (al) are glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol, and sugars, such as glucose.

The compounds having Formula (II) which are used in the hyperbranched dendrimer can be reaction products of alkanolamines (a2) or alkylamines (a3) with carboxylic acids (b1) or with alkyl isocyanates (b2). Non-limiting examples of alkanolamines (a2) are 2-amino-2,3-propanediol, 2-amino-2-methyl-1,3-propanediol, diethanolamine, dipropanolamine, diisopropanolamine, ethanolpropanolamine, triethanolamine, triisopropanolamine, N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine, aminoethylethanolamine, aminopropylethanolamine, alkyltris(hydroxyethyl)propylenediamine and alkyldihydroxyethylamine having preferably from about 12 carbon atoms to about 24 carbon atoms in the alkyl moiety, and also alkoxylation products thereof.

Non-limiting examples of alkylamines (a3) are bis(aminoethyl)amine, bis(aminopropyl)amine and their polymeric homologues, aminoethylaminepropylamine, bis(aminopropyl)ethylenediamine, tris(aminoethyl)amine, tris(aminopropyl)amine, trisaminononane, aminopropylstearylamine, and aminopropylbisstearylamine.

A compound of the present invention can be prepared using mixtures of the mono- and polyhydroxy alcohols (a1) mentioned with the alkanolamines (a2) and with the alkylamines (a3).

The carboxylic acids (b1) used for preparing compound of the Formula (I) or Formula (II) can be saturated, linear or branched chained having any number of carbon atoms, for example, from 9 carbon atoms to 31 carbon atoms, or from 11 carbon atoms to 23 carbon atoms. Non-limiting examples of the saturated linear carboxylic acids used in Formula (I) or Formula (II) include capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid.

The alkyl isocyanates (b2) used for preparing a compound of Formula (I) or Formula (II) can be linear, and have, for example, from 9 carbon atoms to 31 carbon atoms, or from 12 carbon atoms to 22 carbon atoms in the alkyl moiety, an example being stearyl isocyanate.

In lieu of compound prepared using the polyhydroxy alcohols (a1) or the alkanolamines (a2) or the alkylamines (a3) and also the carboxylic acids (b1) or the alkyl isocyanates (b2), the partially-blocked or non-blocked di-, tri- or polyisocyanates can also be reacted with components having an active hydrogen atom and two hydrophobic moieties, for example, Guerbet alcohols, bis(dodecyl)amine, or bis(octadecyl)amine.

The partially-blocked or non-blocked di-, tri- or polyisocyanate can also be reacted using mixtures of two compounds of Formula (I) and Formula (II).

Non-limiting examples of di-, tri- or polyisocyanates include 2,4-tolylene diisocyanate, 2,4′-diphenylmethane diisocyanate, 4-methylcyclohexane 1,3-diisocyanate, 4,4′-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates and polymeric homologs of diphenylmethane diisocyanates (polymeric MDI), tetramethylene diisocyanate, tetramethylene diisocyanate trimers, hexamethylene diisocyanate, hexamethylene diisocyanate trimers, isophorone diisocyanate, isophorone diisocyanate trimers, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate and dimer diisocyanate.

Cyclized oligo- or polyisocyanates can be prepared from the di-, tri- and polyisocyanates mentioned by linking through urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretoneimine, oxadiazinetrione or imineoxadiazinedione structures. Non-limiting examples include hexamethylene diisocyanate trimers, diphenylmethane diisocyanate trimers, and urethanes from 2,4-tolylene diisocyanate, which still have free isocyanate groups.

Some of the isocyanate groups can be reacted with polyalkoxymonoalkyl ethers using appropriate catalyst systems for assistance to form urethanes to improve the emulsifiability of the hyperbranched dendrimer. Polyethylene glycol monomethyl ethers having, for example, from 4 ethylene oxide units to 30 ethylene oxide units, can be used. Non-limiting examples of catalysts include systems based on tertiary amines or organotin compounds, for example dibutyltin dilaurate, dioctyltin dilaurate, and dioctyltin diacetate.

The compounds having Formula (I) or Formula (II) can be reacted with partially-blocked or non-blocked di-, tri- or polyisocyanates to form a dendrimer subunit. In certain embodiments, the dendrimer subunit is a polyurethane dendrimer subunit. In certain embodiments, the dendrimer is a hyperbranched dendrimer comprising dendrimer subunits. In certain embodiments, the hyperbranched dendrimer is a hyperbranched polyurethane dendrimer.

As an alternative to the isocyanates modified with polyalkoxymonoalkyl ethers, tertiary alkanolamines can be used as additives to improve the cationic charge of the dendrimer subunits and hence the self-emulsifying properties without impairing the overall properties. Non-limiting examples include dimethylaminoethanol.

When partially-blocked di-, tri- or polyisocyanates are used for the reaction to form the hyperbranched dendrimer, these compounds can be partially-blocked with, for example, sodium bisulphite, methyl ethyl ketoxime, or 3,5-dimethylpyrazole to effect partial or complete blocking.

Partial blocking can be effected by reacting the di-, tri- or polyisocyanates to be blocked with the blocking agent in the melt or in a substantially isocyanate-inert organic solvent, for example, under a protective gas atmosphere and in the presence of a suitable catalyst. The ratio of the free isocyanate groups of the di-, tri- or polyisocyanates to be blocked to the reactive groups of the blocking agent can be, for example, in a stoichiometric excess up to 2:1 or up to 3:1.

Non-limiting examples of inert organic solvents include anhydrous esters, for example ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, and amyl acetate.

Non-blocked di-, tri- or polyisocyanates can be used as booster polymers, and the self-emulsifiability in water of these non-blocked di-, tri- or polyisocyanates can be enhanced by partial reaction of the isocyanate groups with polyalkoxymonoalkyl ethers through assistance of appropriate catalyst systems to form urethanes. The attachment of hydrophilic side chains to the di-, tri- or polyisocyanates serves to modify the hydrophilic-lipophilic balance value of the resultant urethane such that a water-insoluble compound acquires self-emulsifying properties. Polyethylene oxide can be used, for example, using from about 4 ethylene oxide moieties to about 26 ethylene oxide moieties. The groups can also be present in blocks within the alkoxy chain. In the case of such mixed alkoxylated side chains, the ethylene oxide fraction can outweigh, be outweighed by, or be equivalent in weight to the propylene oxide fraction. Non-limiting examples of catalysts for the urethane synthesis include systems based on tertiary amines or organotin compounds, for example dibutyltin dilaurate, dioctyltin dilaurate, anddioctyltin diacetate.

Urethanes thus prepared can spontaneously from finely-dispersed emulsions in water, which possess high stability to shearing forces and good compatibility with the other components of an application liquor. Owing to the reactivity of the remaining, unconverted isocyanate groups with water, these specialty forms can have limited pot lives of, for example, not more than 8 hours in an application liquor.

The compositions of the present disclosure can be based on water (aqueous based), based on water and organic solvents, and based on organic solvents.

Emulsifiers may be used with aqueous based compositions. Non-limiting examples of emulsifiers include ethoxylation products of fatty acids, fatty acid amides, fatty alcohols, fatty amines, or salts thereof, for example, with low molecular weight organic acids or mineral acids or quaternary ammonium compounds, for example cetylbenzyldimethylammonium chloride or ethoxylated octadecylmethylammonium chloride.

The emulsions of the PTFE can be prepared, for example, by emulsion polymerization or by polyurethane synthesis. The emulsions of the hyperbranched dendrimer can be prepared using secondary emulsions. The emulsifying temperature can be above the melting range of the hyperbranched dendrimer, and can be, for example, from about 50° C. to about 80° C. To produce very finely-dispersed and particularly stable emulsions, a coarsely dispersed pre-emulsion can be prepared first, the particles of which are subsequently comminuted to an average particle size, for example, from about 0.1 micrometers to about 10 micrometers by high pressure homogenizers.

If desired, the inert organic solvents added as a reaction medium for preparing the hyperbranched dendrimer can be distillatively removed after emulsification to avoid the introduction of volatile hydrocarbons into a textile, fabric, or garment.

Non-limiting examples of suitable solvents include ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate and amyl acetate.

The hyperbranched dendrimer and comb polymer can be prepared in an organic solvent, for example ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate or amyl acetate.

In certain embodiments, to apply a composition generated from organic solvents, the solvents used in the preparation of the components of the composition can be chosen such that active substances of the components dissolved in the solvents remain dissolved in the application solvents on further dilution.

Textile materials can be treated to add-ons of, for example, 0.1-5 percent by weight or 0.1-3 percent by weight of solids of a treatment composition based on the weight of the flat material to be treated. An aqueous liquor can be forcedly applied by padding in the desired concentration at wet pick-ups of, for example, 40-100 percent by weight, subsequent predrying at, for example, 80-110° C., and a following hot treatment at, for example, 130-170° C. for 1-5 minutes. An exhaust process can also be used. Application can further be carried out by spray application, brush application, sponge application, drenching, or dripping.

The compositions of the present invention can be combined with textile auxiliaries. Non-limiting examples include methylol compounds of dihydroxyethyleneurea or methylolmelamine ethers having different degrees of methylolation. Useful textile auxiliaries further include those which improve flame resistance or endow the flat material with a hand which is desired by the customer (e.g., softness, fullness, smoothness, etc.).

A revitalizing treatment of a garment that has lost any of the desired properties takes place in a washing or spin dryer drum by pouring a liquor of the compositions according to the present invention on the moist spun garments and subsequent tumble drying. In the case of household washing machines, the finish can be applied in the course of the customary rinse cycle or by means of a dosing ball system.

A further aspect of the present disclosure is the use of the compositions as a finish on flat materials from organic solvents by drenching or dipping.

The revitalizing treatment of garments cleaned in organic solvents can take place in the cleaning drum of a dry cleaning machine by pouring or spraying a liquor of the compositions according to the present invention onto the solvent wet cleaned articles and subsequent removal of the solvents in a tumble dryer at elevated temperatures.

Water repellency may be scored according to 0-10 scale (with 0 being the lowest and 10 being the highest degree of water repellency) according to the 3M Water Repellency Test II. Oil repellency may be scored according to 0-8 scale (with 0 being the lowest and 8 being the highest degree of oil repellency) based on ISO 14419:2010. In certain embodiments, a treated textile can have a water or oil repellency of about 1, about 2, about 3, about 4, about 5, about 6, about 7, or about 8. In certain embodiments, a treated textile can have a water or oil repellency from about 1 to about 2, from about 2 to about 3, from about 3 to about 4, from about 4 to about 5, from about 5 to about 6, from about 6 to about 7, or from about 7 to about 8.

In certain embodiments, a composition may be soil-repellent or soil-resistant, and may be repellent of or resistant to plant-based food articles, including, but not limited to, tomato sauce, chili sauces (e.g., sriracha), or other sauces containing capsaicin or mustard oil.

In certain embodiments, a treated textile will have a detectable amount of fluorine or an impurity of the composition. Non-limiting examples of impurities include alkylphenol ethoxylates, phthalate plasticizers, azo dyes, organotin compounds, antimony, or isocyanates.

In certain embodiments, a treated textile can have a concentration of fluorine or an impurity of about 1 parts per million (ppm), about 2 ppm, about 3 ppm, about 4 ppm, about 5 ppm, about 6 ppm, about 7 ppm, about 8 ppm, about 9 ppm, about 10 ppm, about 15 ppm, about 20 ppm, about 30 ppm, about 40 ppm, about 50 ppm, about 60 ppm, about 70 ppm, about 80 ppm, about 90 ppm, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, or about 1000 ppm.

In certain embodiments, a treated textile can have a concentration of fluorine or an impurity from about 1 ppm to about 2 ppm, from about 2 ppm to about 3 ppm, from about 3 ppm to about 4 ppm, from about 4 ppm to about 5 ppm, from about 5 ppm to about 6 ppm, from about 6 ppm to about 7 ppm, from about 7 ppm to about 8 ppm, from about 8 ppm to about 9 ppm, from about 9 ppm to about 10 ppm, from about 10 ppm to about 15 ppm, from about 15 ppm to about 20 ppm, from about 20 ppm to about 30 ppm, from about 30 ppm to about 40 ppm, from about 40 ppm to about 50 ppm, from about 50 ppm to about 60 ppm, from about 60 ppm to about 70 ppm, from about 70 ppm to about 80 ppm, from about 80 ppm to about 90 ppm, from about 90 ppm to about 100 ppm, from about 100 ppm to about 200 ppm, from about 200 ppm to about 300 ppm, from about 300 ppm to about 400 ppm, from about 400 ppm to about 500 ppm, from about 500 ppm to about 600 ppm, from about 600 ppm to about 700 ppm, from about 700 ppm to about 800 ppm, from about 800 ppm to about 900 ppm, or from about 900 ppm to about 1000 ppm.

In certain embodiments, a treated textile has an oil repellency of about 4 or greater, a water repellency of about 4 or greater, and a fluorine concentration by weight of treated fabric from about 20 ppm to about 500 ppm. The textile substrate can be treated with an aqueous dispersion of surface treated particles and a fluorochemical. A treated textile can have a fluorochemical chemically bound to the surface of inorganic particles and said surface of said inorganic particles can be surface-modified with a polymer, cationic inorganic sol, silane coupling agent, or hydrolyzed precursor of a silane coupling agent.

In certain embodiments, an aqueous dispersion for treating surfaces imparts water repellency and oil repellency, the aqueous dispersion comprising surface functionalized inorganic particles, made of metal oxide particles, ranging in size from about 2 nanometers (nm) to about 500 nm, that have been surface functionalized with a surface functionalizing agent, are stably suspended in an aqueous medium with a fluorochemical chemically bound to the surfaces of the functionalized particles.

In certain embodiments, a treated textile is stain resistant and water and oil repellent, which has been made by treatment with an aqueous dispersion comprising; water, surface-functionalized inorganic particles, fluorochemicals and optionally, a cross-linking agent, and optionally, a hydrophobic polymer, wherein the fluorine concentration by weight per weight of treated textile fabric is from about 20 ppm to about 500 ppm.

In certain embodiments is provided an aqueous dispersions used to treat textiles. These dispersions are stable dispersions of functionalized inorganic particles with chemically bound fluorochemical. The inorganic particles can be from about 2 nm to about 500 nm, surface functionalized with a surface functionalizing agent, and stably suspended in an aqueous medium.

Further treated textiles according to the present invention can have oil and water repellencies greater than 6, and fluorochemical concentration from about 20 ppm to about 900 ppm.

In certain embodiments, the treated textiles are the product of treating textiles in order to impart water and oil repellency by contacting textiles with the aqueous dispersion and then fixing the particles of the dispersion to the textile surfaces. Fixing the particles to the textile can involve using cross-linkers to chemically bind the particles to the textile surface.

The surface-functionalized inorganic particles can be metal-oxide or metal oxy-hydroxide particles having a mean particle diameter from about 2 nm to about 500 nm. In certain embodiments, the particles have a mean particle diameter from about 5 nm to about 250 nm, for example, from about 10 nm to about 100 nm. The metal-oxide inorganic particles can be silica, alumina, zirconia, titania, zinc oxide, or other types of particles. Specific examples include colloidal, precipitated, or fumed silica, aluminas, such as Al₂O₃ and polymorphs thereof, AlOOH, ZrO₂ and oxy-hydroxide derivatives and related metal salts and derivatives thereof, TiO₂, and ZnO. In certain embodiments, other suitable materials include mixed metal oxyhydroxides and clay minerals such as layered double hydroxides, hydrotalcite, smectic clays, hydroxy double salts, and layered siliceous materials. Non-limiting examples include: layered double hydroxides (related to the mineral hydrotalcite) of the general formulas: [M²⁺ _(1-x)M³⁺ _(x)(OH)₂]A^(n−) _(x/n).yH₂O or [M¹⁺M³⁺ ₂(OH)₆]A^(n−) _(x/n).yH₂O, wherein M¹⁺ is Li or Na; M²⁺ is Ca or Mg; and M³⁺ is Fe or Al; A is NO₃ ⁻, Cl⁻, or CO₃ ²⁻, and layered siliceous materials such as natural or synthetic clay minerals exemplified by montmorillonite, bentonite, kaolin, vermiculite, talc, and saponite, given by the general formula: [M1,M2]_(n)Z₄O₁₀(OH)_(2y)H₂O₂; wherein M1 is typically Al or Fe, M2 is typically Mg or Zn; and Z is Al or Si.

The surfaces of the inorganic metal-oxide particles of the invention can be functionalized with inorganic, polymeric, or molecular species. The functionalized surfaces serve to convert the surface characteristics of the particles from hydrophilic to hydrophobic and, further, to provide a functionality such that the particles can be cross-linked (chemically bound) to the textile article or to reactive sites on the fluorochemical. Cross-linking serves to provide durability to the finish such that the stain and water/oil repellent properties survive launderings, weather (for outdoor fabrics), use and abrasion, etc.

The surfaces of the inorganic metal-oxide or metal(oxy)hydroxide particles can be functionalized using surface functionalizing agents. The surface functionalizing agents can be chemically linked to the particle either through covalent bonding, or through charge attraction. The surface functionalizing agents can contain a “functional group” that is free to react with functional groups on the surfaces of the fabric, or with polymeric addenda in the treatment solution such as fluorochemicals, aliphatic polymers, resins or waxes. Suitable functional groups, capable of forming chemical bonds with the fabric or with polymeric addenda, include carboxylate groups, hydroxyl groups, amine groups, amide groups, and thiol groups. Suitable functional groups also include complexing inorganic metals or complexes such as aluminates, silicates and zirconates.

In certain embodiments are provided cationic inorganic sols of aluminum and zirconium, such as aqueous solutions of ZrOCl₂, ZrO(NO₃)₂, ZrO(OH) acetate, and Al₂(OH)₅Cl. The particles can also be surface-functionalized with polymers, especially amine-containing polymers such as polyethylenimine, polyallylamine, or polyamides, and siloxane polymers having amine or amide functionalities. Amine containing polymers can attach to the surface of silica particles via charge attraction upon protonation of the amine at a pH less than about 8.

Particles herein can have surfaces functionalized by silane coupling agents, or hydrolyzed precursors of silane coupling agents having the general formula: R_(a)R′_(b)Si(OR″)_(4−(a+b)); wherein a and b are integers from 1 to 3, (a+b) is less than or equal to 3, R and R′ are organic groups having from 1 to 30 carbon atoms and R″ is H, or an organic group having from 1 to 6 carbon atoms.

Alternatively, the silane coupling agent may have the general formula: R_(a)Si(X)_(4−a); wherein a and R are as defined above and X is Cl, Br or I.

Non-limiting examples of silane coupling agents include 3-chloropropyl(trimethoxy)silane, 3-chloropropyl(triethoxy)silane, 3-chloropropyldimethylmethoxysilane, 3-chloropropyltris(trimethylsiloxy)silane, 3-mercaptopropyl(trimethoxy)silane, 3-mercaptopropylmethyl(diethoxy)silane, methacryloxypropyl(trimethoxy)silane, 2-[methoxy(polyethyleneoxy)propyl](trichloro)silane, 2-[methoxy(polyethyleneoxy)propyl](trimethoxy)silane, octyl(trimethoxy)silane, octadecyl(trimethoxy)silane, 3-isocyanatopropyldimethylchlorosilane, 3-isocyanatopropyl(triethoxy)silane, Bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, aminopropylsilanetriol, 3-aminopropyl(triethoxy)silane, 3-aminopropyl(trimethoxy)silane, N-(2-aminoethyl)-3-aminopropylsilalletriol, N-(2-aminoethyl)-3-aminopropyl(trimethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, isopropyl(trimethoxy)silane, (3-glycidoxypropyl)methyldimethoxysilane, tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, (3-trimethoxysilylpropyl)diethylenetriamine, and octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride.

An aqueous dispersion can comprise metal oxide or metal oxy hydroxide nanoparticles that are surface functionalized with a surface functionalizing agent. The surface functionalizing agent can be applied to the surfaces of said nanoparticles by mixing the nanoparticles with the surface functionalizing agent at an appropriate ratio in a high speed or high shear mixing apparatus. The appropriate ratio can be determined by measuring the saturation adsorption of the surface functionalizing agent on the nanoparticles. The saturation absorption describes the maximum number of surface functionalizing agents that can be adsorbed, or bound to, the particle surfaces per unit surface area, and has the units μmol/m². Saturation adsorptions can vary, for example, from about 0.5 μmol/m² to about 5 μmol/m². The nanoparticles and the surface functionalizing agent can be brought together at a ratio very near the saturation absorption, for example, from about 80 percent to about 120 percent of that value, or from about 90 percent to about 110 percent of that value.

To initiate the surface functionalization reaction, the nanoparticles and the surface functionalizing agent can be mixed together in a high-shear mixing zone within a dispersion medium. The high-shear mixing zone can be provided by a propeller-like mixer, a static mixer, an in-line mixer, a dispersator, or another high-shear mixing apparatus. The mixing efficiency of the apparatus can be dependent upon the type of mixing method chosen and the precise geometry and design of the mixer.

Fluorochemicals can impart stain and oil/water resistance to textile fabrics. Non-limiting examples of fluorochemicals include any of the organo-fluorine group-containing organic compounds, including polymeric and oligomeric compounds. These polymeric and oligomeric compounds can contain one or more organo-fluorine groups that contain a perfluorinated carbon chain having, for example, from about 3 to about 16 carbon atoms, or, for example, from about 4 to about 8 carbon atoms. The organo-fluorine groups can be straight-chained, branched, or cyclic fluorinated alkyl or alkylene groups.

Fluorochemicals can contain non-fluorinated co-monomers. Non-limiting examples of non-fluorinated co-monomers include methyl methacrylate, dodecylmethacrylate, octadecylmethacrylate, butyl acrylate, and polyvinylchloride. The non-fluorinated co-monomers can also contain hydrophilic groups to aid in the dispersibility of the polymer in aqueous solution, for example, polyethyleneglycol-methacrylates and -acrylates, and 2-hydroxyethylacrylate.

Fluorochemicals can contain one or more cross-linkable moieties capable of forming covalent bonds with functionalities on the surfaces of the individual fibers of the fabric. The functional group can react directly with functionalities on the surface of the individual fibers or may react with a cross-linker. Non-limiting examples of cross-linkable moieties include carboxylate groups, hydroxyl groups, amine groups, amide groups, and thiol groups. Examples of cross-linkers include melamine resins, isocyanates and polyisocyanates.

ILLUSTRATIVE EXAMPLES

The following examples are set forth to assist in understanding the invention and should not, of course, be construed as specifically limiting the invention described and claimed herein. Such variations of the invention, including the substitution of all equivalents now known or later developed, which would be within the purview of those skilled in the art, and changes in formulation or minor changes in experimental design, are to be considered to fall within the scope of the invention incorporated herein.

Example 1 Preparation of a Composition for Water Repellency

An example procedure for the preparation of a composition of the disclosure is as follows. A liquor of about 30-60 g (e.g., 50 g) RUCO DRY ECO® is prepared in about 1 L water, for example, soft water or hard water, at pH of about 3.5 to about 5.5 (e.g., about 4.5). The RUCO DRY ECO® is added to the water at room temperature through a finely-meshed sieve or filter. Another additive is incorporated into the liquor. The liquor is then adjusted by addition of about 0.5 mL 60% acetic acid to the liquor. Throughout the preparation process, the liquor is stirred by magnetic spinning.

Example 2 Spray Treatment of a Cotton Material with a Composition for Water Repellency

FIG. 1 illustrates a method 100 for treating a material (e.g., a cotton material) with a treatment composition of the disclosure (e.g., of Example 1) using a sprayer. Prior to treatment, at block 101, the material is subjected to an anionic pre-wash to remove possible contaminants, including residual alkali, multivalent salts, and surface-active residues such as emulsifiers from the cotton. At block 102, the treatment composition is forcedly applied to the material (e.g., sprayed). In certain embodiments, the treatment composition is applied via spraying using a NorthStar ATV Boomless Broadcast and Spot sprayer. In certain embodiments, a booster polymer is added to the treatment composition prior to being applied to the material to increase water-repellent effects. At block 103, after application of the treatment, the cotton material is allowed to set. After the setting, at block 104, the treated material is pre-dried, (e.g., at about 100° C.). At block 105, the treated material is subjected to a hot dry (e.g., at about 170° C. for about 30 seconds). The treated material is then machine washed at block 106, followed by machine drying and ironing at block 107. In certain embodiments, the machine drying is performed at greater than about 65° C., and ironing occurring at customary laundry temperatures. In certain embodiments, the treatment may be performed again if the treatment does not successfully penetrate the material. In such embodiments, the method 100 proceeds to block 108, where a wetting agent is applied to the material (e.g., about 10 grams, or another suitable quantity), and the method 100 proceeds to block 101.

Example 3 Treatment of a Wool Fabric with a Composition for Water Repellency in a Dyeing Machine

FIG. 2 illustrates a method 200 for manufacturing a fabric (e.g., wool) treated with a composition of the disclosure (e.g., of Example 1) in a dyeing machine. At block 201, the fabric undergoes singeing to remove loose, hairy, or projecting wool fibers from the fabric. After singeing, at block 202, the fabric undergoes de-sizing to remove gummy and size materials from the fabric. After de-sizing, at block 203, the fabric undergoes scouring to remove impurities. In certain embodiments, the scouring is an anionic pre-wash to remove contaminants, including residual alkali, multivalent salts, and surface-active residues such as emulsifiers from the wool. After scouring, at block 204, the fabric undergoes bleaching to reduce the natural color of the fabric, which improves the efficiency of dyeing. After bleaching, at block 205, the fabric undergoes mercerizing to increase the strength and luster of the fabric. After mercerizing, at block 206, the fabric undergoes dyeing, e.g., in a Thies rotoMaster rolling drum dyeing machine, to apply the composition to the fabric. In certain embodiments, an LK ST Stenter machine is used to apply the composition to the fabric. After dyeing, at block 207, the fabric undergoes drying. In certain embodiments, the drying occurs at about 160° C. for about 1 minute.

Example 4 Treatment in a Dyeing Machine of a Cotton Yarn Material with a Composition for Water Repellency

FIG. 3 illustrates a method 300 for manufacturing a yarn (e.g., cotton) treated with a composition of the disclosure (e.g., of Example 1) in a dyeing machine. At block 301, the cotton yarn is wound onto a spring tube, which is then loaded and pressed to a desired height onto a dyeing carrier spindle at block 302. At block 303, the dyeing carrier spindle is then loaded onto a Theis eco-bloc quattro yarn dyeing machine. At block 304, the yarn is then machine treated with the composition and transferred to an Electrolux C290R rigid mount hydro extractor at block 305, where the hydro extractor removes any excess water from the treated yarn. After water extraction by the hydro extractor, at block 306, the treated yarn is dried (e.g., at about 160° C. for about 1 minute).

Example 5 Treatment in a Rolling Machine of a Cotton/Wool Blend Garment with a Composition for Water Repellency

FIG. 4 illustrates a method 400 for manufacturing a garment (e.g., a cotton/wool blend garment) treated with a composition of the disclosure (e.g., of Example 1) in a dyeing machine. At block 401, the garment undergoes scouring to remove impurities. In certain embodiments, the scouring is an anionic pre-wash to remove contaminants, including residual alkali, multivalent salts, and surface-active residues such as emulsifiers from the garment. After scouring, the garment undergoes dyeing, e.g., in a Thies rotoMaster rolling drum dyeing machine, to apply the composition to the garment. After dyeing, at block 403, the garment undergoes drying 403. In certain embodiments, the drying 403 occurs at about 150° C. for about 2 minutes. After drying, at block 404, if any of the desired properties of the garment are lost, a revitalizing treatment of the garment is performed using a UniMac® UW Series Hardmount Washer-Extractor washing machine by pouring a liquor of the composition on the moist spun garments and performing subsequent tumble drying.

In the foregoing description, numerous specific details are set forth, such as specific materials, dimensions, processes parameters, etc., to provide a thorough understanding of the embodiments of the present disclosure. The particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments. The words “example” or “exemplary” are used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as “example” or “exemplary” is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the words “example” or “exemplary” is intended to present concepts in a concrete fashion. As used in this application, the term “or” is intended to mean an inclusive “or” rather than an exclusive “or”. That is, unless specified otherwise, or clear from context, “X includes A or B” is intended to mean any of the natural inclusive permutations. That is, if X includes A; X includes B; or X includes both A and B, then “X includes A or B” is satisfied under any of the foregoing instances. In addition, the articles “a” and “an” as used in this application and the appended claims should generally be construed to mean “one or more” unless specified otherwise or clear from context to be directed to a singular form.

Reference throughout this specification to “an embodiment”, “certain embodiments”, or “one embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrase “an embodiment”, “certain embodiments”, or “one embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment, and such references mean “at least one”.

It is to be understood that the above description is intended to be illustrative, and not restrictive. Many other embodiments will be apparent to those of skill in the art upon reading and understanding the above description. The scope of the disclosure should, therefore, be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. 

What is claimed is:
 1. A method of manufacturing comprising: treating a textile with a composition, the composition comprising: (1) polytetrafluoroethylene; and (2) a dendrimer.
 2. The method of claim 1, wherein the dendrimer is hyperbranched.
 3. The method of claim 2, wherein the hyperbranched dendrimer is a hyperbranched polyurethane dendrimer.
 4. The method of claim 1, wherein the composition further comprises a comb polymer.
 5. The method of claim 1, wherein the composition further comprises an emulsifier.
 6. The method of claim 1, wherein the textile is a cotton or a wool.
 7. The method of claim 1, wherein the textile is selected from a group consisting of a yarn, a blend, a fabric, a garment, an upholstery, or combinations thereof.
 8. The method of claim 1, wherein the treatment is performed with a sprayer.
 9. The method of claim 1, wherein the treatment is performed by a dyeing machine or a rolling drum dyeing machine.
 10. The method of claim 1, further comprising treating the textile with a booster polymer prior to treating the textile with the composition.
 11. The method of claim 1, further comprising, after treating and drying of the textile: treating of the textile with a wetting agent; additional treating of the textile with the composition; and additional drying of the textile.
 12. A treated textile comprising: a textile and a composition comprising: polytetrafluoroethylene; and a dendrimer.
 13. The treated textile of claim 12, wherein the dendrimer is hyperbranched.
 14. The treated textile of claim 13, wherein the hyperbranched dendrimer is a hyperbranched polyurethane dendrimer.
 15. The treated textile of claim 12, wherein the composition further comprises a comb polymer.
 16. The treated textile of claim 12, wherein the comb polymer is modified with a wax.
 17. The treated textile of claim 12, wherein the composition further comprises an emulsifier.
 18. The treated textile of claim 12, wherein the textile is a cotton or a wool.
 19. The treated textile of claim 12, wherein the textile is selected from a group consisting of a yarn, a blend, a fabric, a garment, an upholstery, or combinations thereof.
 20. A treated textile treated with a composition comprising: polytetrafluoroethylene; a dendrimer; a comb polymer; and an emulsifier. 